Synthesis and Reactivity of Dinuclear Complexes Containing η2-Phenyl−Metal Interactions. Crystal Structures of [NBu4][(C6F5)3Pt{μ-Ph2PCH2PPh(η2-Ph)}Pt(C6F5)2] and [NBu4][(C6F5)3Pt(μ-dppm)Pt(C6F5)2(CO)]

Reaction between [NBu 4 ][Pt(C 6 F 5 ) 3 (dppm-κ 1 P)] and cis- [M(C 6 X 5 ) 2 (thf) 2 ] (M = Pt, Pd; X = F, Cl; thf = tetrahydrofuran) leads to dinuclear derivatives with dppm ligands bridging two metal centers: [NBu 4 ][(C 6 F 5 ) 3 Pt{μ-Ph 2 PCH 2 PPh(η 2 -Ph)}M(C 6 X 5 ) 2 ] [X = F, M = Pt ( 1 ), M = Pd ( 2 ); X = Cl, M = Pt ( 3 ), M = Pd ( 4 )]. The structural characterization of complex 1 by single-crystal X-ray diffraction (orthorhombic system, space group Fdd 2, with a = 26.520(7) Å, b = 83.69(3) Å, c = 13.835(5) Å, V = 30706(11) Å 3, and Z = 16) reveals two square-planar platinum(II) fragments sharing a dppm ligand with a η 2 -phenyl−platinum interaction between a phenyl ring of the dppm ligand and one platinum center. This weak η 2 -phenyl−platinum interaction can be easily displaced by addition of ligands such as CO (giving complex 5 ), PPh 3 ( 6 ), or p -toluidine ( 7 ). The structure of 5 was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group Pn, with a = 12.259(2) Å, b = 16.375(3) Å, c = 18.851(4) Å, β = 100.99(3)°, V = 3714.8 Å 3, and Z = 2. The complex consists of two square-planar platinum(II) fragments with the dppm ligand acting as a conventional bridge.